Raphael was one of the four archangels created by God. He was older than Gabriel but younger than Michael and Lucifer.
In Season 4, Raphael (his presence only) protected Chuck from Lilith's harm and then tried to stop Dean and Castiel from stopping Sam from breaking the last seal and killed Castiel. In Season 5, he became a target of Castiel, resurrected, and Dean to find God but he didn't have answers and they left him in a ring of holy fire as he vowed to kill the angel.
In Season 6, Raphael escaped and returned to Heaven with the intent of taking over and re-starting the Apocalypse but was opposed by Castiel and a civil war began, forcing Castiel to team up with Crowley to obtain the souls of Purgatory. When Castiel betrayed him, Raphael allied himself with Crowley to obtain the power for himself, only to be killed by the angel when he took the power.

Even a sex change could not help Raphael from his brother Castiel! Raphael was actually one of my favorite Arch Angeles... Hell I like them all lol!
Team Winchester